Toughened Plastics I - American Chemical Society

glass-transition temperatures in the range of — 70 to 0 °C, which depend on the nature ... Although vernonia oil is at a developmental stage, it is...
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Toughening of Epoxy Resins by Epoxidized Soybean Oil Isabelle Frischinger and Stoil Dirlikov 1

Coatings Research Institute, Eastern Michigan University, Ypsilanti, MI 48197

Homogeneous mixtures of a liquid rubber based on prepolymers of epoxidized soybean oil with amines, diglycidyl ether of bisphenol A epoxy resins, and commercial diamines form, under certain conditions, two-phase thermosetting materials that consist of a rigid epoxy matrix and randomly distributed small rubbery soybean particles

(0.1-5

μm). These two-phase thermosets have improved toughness, similar to that of other rubber-modified epoxies, low water absorption, and low sodium content. In comparison to the unmodified thermosets, the two-phase thermosets exhibit slightly lower glass-transition tempera­ tures and Young's moduli, but their dielectric properties

do not

change. The epoxidized soybean oil is available at a price below that of commercial epoxy resins and appears very attractive for epoxy tough­ ening on an industrial scale.

TOUGHENING OF EPOXY RESINS BY AN ELASTOMERIC SECOND PHASE was first demonstrated by Sultan et al. (1, 2). It is now well established that a small amount of discrete rubbery particles that have an average size of several micrometers and are randomly distributed in a glassy brittle epoxy thermoset dissipates part of the impact energy and, thus, improves crack and impact resistance without major deterioration of other properties of the unmodified epoxy thermosets (3, 4). The main role of the rubber phase i n toughened epoxies is to relieve the constraints i n the matrix through the principal mechanisms of cavitation and formation of shear bands (5, 6). This phenomenon is used for industrial-scale toughening of epox^ resins. 1

Current Address: Polymer Division, Ciba-Geigy A.G., CH-4002 Basel, Switzerland

0065-2393/93/0233-0451$10.75/0 © 1993 American Chemical Society

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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RUBBER-TOUGHENED PLASTICS

Epoxy toughness is usually achieved by separation of a rubbery phase that has a unimodal size distribution from the matrix during the curing process. Different reactive liquid rubbers, based on low molecular weight carboxy- or amino-terminated oligomers of butadiene and acrylonitrile [carboxyl-terminated butadiene-acrylonitrile ( C T B N ) and amine-terminated butadiene-acrylonitrile (ATBN)], are usually used for the formation of the rubbery phase. Low molecular weight amino-terminated (methyl) siloxanes offer other alternatives, but some of these oligomers are quite expensive. Epoxidized vegetable oils, such as vernonia, epoxidized soybean (ESO), and linseed oils, open new opportunities. Vegetable oil epoxy resins with commercial diamines are elastomers at room temperature that have low glass-transition temperatures in the range of — 70 to 0 °C, which depend on the nature of the amine used for curing. Epoxidized vegetable oils, however, are characterized by good compati­ bility with polymers, and it appears unlikely that they form a second phase with epoxy resins. Qureshi et al. (7) observed small-scale heterogeneity in epoxy thermosets that contained epoxidized vegetable oils. The broadening of the glass-transition region in dynamic mechanical analysis ( D M A ) with the appearance of small additional loss peaks indicates that these formulations form semimiscible thermosets. In our previous paper (8), we described initial results on toughening of epoxy thermosets with vernonia oil, a natural epoxidized vegetable oil that contains three epoxy rings and three carbon-carbon double bonds:

CH (CH ) CH-CH.CH .CH=CH.(CH ) COOCH 3

2

4

2

2

7

2

Ο

CH (CH ) CH-CH.CH .CH=CH.(CH ) COOCH 3

2

4

2

2

?

Ο CH (CH ) CH-CH.CH .CH=CH.(CH ) COOCH 3

2

4

2

2

?

2

\ / We obtained two-phase thermosets that consisted of a rigid matrix of commercial epoxy resin with randomly distributed small rubbery, spherical vernonia particles. The vernonia particles separate during the curing process from the initial homogeneous mixture of diglycidyl ether of bisphenol A epoxy [Epon resin 825; Shell Chemical Company; 4,4 -diaminodiphenyl methane ( D D M ) or 4,4'-chammodiphenyl sulfone (DDS)] and vernonia liquid rubber, which is a B-staged material (soluble prepolymer) of vernonia oil with D D M or 1,12-dodecanediamine. ,

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

19.

FRISCHINGER AND DIRLIKOV

453

Epoxidized Soybean Oil

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Although vernonia oil is at a developmental stage, it is unavailable for industrial applications. Therefore we are evaluating other epoxidized veg­ etable oils for toughening epoxy resins. The industrially produced epoxidized soybean and linseed oils are available at a low price (in the range of $0.50 to $0.65 per pound), which makes them very attractive. In this chapter, our initial unoptimized results on toughening commercial epoxy resins by epoxi­ dized soybean oil are described. Epoxidized soybean oil consists of a mixture of different triglycerides. The triglyceride structures are schematically illus­ trated by the following formula:

CH (CH ) CH-CH.CH .CH-CH.(CH ) COOCH 3

2

4

2

Ο

2

J

7

2

CH (CH ) .CH-CH.(CH ) COOCH 3

2

7

2

7

Ο CH (CH ) CH-CH.CH .CH-CH.(CH ) COOCH 3

2

4

2

\/

2

7

2

\ /

Experimental Details Materials. The epoxidized soybean oil is produced under the com­ mercial name Flexol Plastieizer E P O (Union Carbide Corporation). The average epoxy functionality of this oil is approximately 4.5. Epon epoxy resin 825, a solid diglycidyl ether of bisphenol A ( D G E B A ) , is a Shell Chemical Company product. A l l amine curing agents were purchased from Aldrich Chemical Company. Epoxidized Soybean Liquid Rubber. The epoxidized soybean liquid rubber (ESR) was prepared by B-staging (prepolymerization) of epoxi­ dized soybean oil with a stoichiometric amount of D D M . For this purpose, a mixture of 100 g of epoxidized soybean oil and 22.28 g of D D M was heated in a nitrogen atmosphere at 135 °C for 37-40 h until a highly viscous liquid, which was still soluble in the commercial D G E B A epoxy resin at 70 °C, was obtained. The slight B-staging time variation from batch to batch was dependent on the quality of the epoxidized soybean oil used. E S R density (1.05 g/cm at 20 °C) was determined with a pyenometer. 3

Cure Procedure. The epoxy formulations are based on stoichiomet­ ric mixtures of D G E B A and amine curing agent ( D D M , D D S , etc.) contain-

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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RUBBER-TOUGHENED PLASTICS

ing 10, 15, 20, and 30 wt % of epoxidized soybean liquid rubber or a stoichiometric mixture of the initial epoxidized soybean oil and amine curing agent. The cure was carried out according to the following procedure: First, the mixture of D G E B A and epoxidized soybean oil or rubber was heated at 75 °C under vacuum with stirring for 15-30 min. Then the stoichiometric amount of the diamine ( D D S , D D M , etc.) was added while stirring. The mixture was degassed and stirred under a vacuum for an additional 15 min at 150 °C for the D D S formulations, or for 30 min at 75 °C for the D D M formulations. Then it was poured into a mold that was preheated at 150 °C for D D S and at 75 °C for D D M formulations, and again left under a vacuum for 15 min. For the D D S formulations, the final cure was carried out in an air-circulating oven at 150 °C for 2 h. D D M formulations were cured first at 75 °C for 4 h and then at 150 °C for 2 h.

Morphology. The morphology of the neat and rubber-modified epoxy resins was examined by scanning electron microscopy ( S E M ) of the fracture surfaces using an electron microscope (Amray model 1000B). Fracture Toughness. Single-edge-notched (SEN) specimens with approximate dimensions of 100 mm long X 12.7 mm wide X 6.7 mm thick (Figure 1) were machined from castings. A sharp crack was introduced into the specimen by the strike of a razor blade (previously chilled in liquid nitrogen) with a rubber mallet. The tests were carried out with a three-point bending assembly, which was monitored by a servohydraulie materials testing machine (Instron 1331) with a span of 50.8 mm and a piston rate of 2.54 mm/s. A computer interface controlled the machine and recorded the data. A computer (Hewlett-Packard model 310) was programmed to calculate the

P/2

P/2

Figure 1. Single-edge-notched (SEN) specimen used for determination of fracture toughness by the three-point bending test The dimensions are in millimeters.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

19.

455

FRISCHINGER AND DIRLIKOV Epoxidized Soybean Oil

critical stress intensity factor, K , using the relation (9) I c

2 PS να"

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where Ρ is the critical load for crack propagation in Newtons (N), S is the length of the span (mm), a is the crack length (mm), w is the width (mm), t is the thickness (mm), and Y is the nondimensional shape factor given by Y = 1.9 — 3.07(α/α>) + U.53(a/w)

- 25.U(a/w)

2

3

+

25.80(a/w)

4

The following simple relationship, which holds in our case of linearelastic-fracture mechanics ( L E F M ) under plane strain conditions, was used for determination of the fracture energy, G : I C

(l-v )(K 2

G

I c

=

I c

)

2

where ν is the Poisson s ratio and Ε is the elastic or Young's modulus. At least eight specimens of each formulation were used for determination of average fracture energy G . I c

Uniaxial Tensile Test. Dog-bone bars with dimensions of 6 in. X 0.5 in. X 1/8 in. (152 mm X 12.7 mm X 3.5 mm) were cut with a high speed router and their external surface was polished with very fine aluminum oxide sandpaper 220 (3M Corporation). A screw-driven tensile tester (Instron model 1185), equipped with an extensometer for determination of the longitudinal strain and a computer interface type 4500 series, was used at a stroke rate of 60 mm/min. At least 10 specimens of each formulation were used for determination of the average tensile properties at room temperature. Dynamic Mechanical Analysis. A thermal analyzer (DuPont 2100) instrument with dynamic mechanical analysis ( D M A ) model 983, based on a flexural bending deformation measurement, and rectangular bar specimens with approximate dimensions of 45 mm X 7.8 mm X 3.5 mm were used to study the dynamic mechanical properties over the temperature range from - 1 3 0 to 200 °C at a heating rate of 2 °C/min. Differential Scanning Calorimetry. Differential scanning calorimetry (DSC) measurements were carried out on a thermal analyzer (DuPont 2100) instrument with D S C model 2910 over the temperature range from - 1 3 0 to 200 °C at a heating rate of 2 °C/min.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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RUBBER-TOUGHENED PLASTICS

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Water Absorption. Maximum water absorption was determined on rectangular specimens with approximate dimensions of 45 mm X 7.8 mm X 3.5 mm, which were predried in a vacuum oven at 60 °C to constant weight and then kept i n boiling water for 3 - 4 weeks until saturation (e.g., to constant weight). Dielectric Properties. The dielectric constant and dissipation factor were measured at 1 M H z and room temperature on 3 in. X 3 in. X 1/8 in. specimens on a dielectric analyzer Genrad 1687 Β Digibridge equipped with an L D - 3 cell and using the two-fluid method (air and D C - 2 0 0 ; 1 cs). Gel Permeation Chromatography. Gel permeation chromatogra­ phy (GPC) was measured on a G P C instrument (Hewlett-Packard) with a differential refractometer (Waters Associates model R401) and gel columns (Polymer Laboratory). Infrared Spectroscopy. Infrared spectra were taken with an in­ frared spectrometer ( I B M 44).

Sodium Content. The epoxidized soybean oil and rubber samples were first dissolved by acid digestion. Sodium content was determined with an atomic absorption spectrophotometer (Perkin-Elmer 2380). Our results were confirmed by sodium analysis at Galbraith Analytical Laboratory. Results and Discussion Morphology. The morphology of the two-phase D G E B A - s o y b e a n epoxy thermosets was evaluated by scanning electron microscopy as an average of several micrographs taken at different fracture surfaces for each formulation. Our primary interest was to elucidate the evolution process of the second (liquid or rubbery) phase and particle size determination. There­ fore, we studied the dependence of morphology on the weight percentage of soybean fraction and on the compatibility of the formulations: polarity of the diamine curing agent, degree of B-staging of the epoxidized soybean oil, and so forth. The commercial epoxy resin used in the present study is Epon resin 825, which is practically pure D G E B A . Most of the research was done with stoichiometric D D M or D D S formulations of D G E B A . Only initial screening evaluation was carried out on D G E B A formulations with other cycloaliphatic (isophorone diamine) and aliphatic diamines and polyamines (1,10-decanediamine, 1,12-dodecanediamine, diethylenetriamine, triethylenetetramine, etc.). These epoxy-amine formulations were toughened by the addition of 10, 15, 20 and 30% of epoxidized soybean oil or liquid rubber (prepolymer) as described in the "Experimental Details" section.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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19.

FRISCHINGER AND DIRLIKOV Epoxidized Soybean Oil

457

Initial attempts to toughen epoxy resins were carried out directly with epoxidized soybean oil. For this purpose, homogeneous mixtures of D G E B A and diamine ( D D M , isophorone diamine, different aliphatic di- and polyamines, etc.) that contained 10-30% epoxidized soybean oil were cured according to a conventional curing procedure for epoxy resin at 70 °C. Because the diamines have a much higher reactivity with D G E B A than with the epoxy groups of the epoxidized soybean oil, they form a rigid matrix at 70 °C in which the epoxidized soybean oil separates as a second phase of small liquid droplets. The electromicrograph of such a thermoset based on D G E B A , isophorone diamine, and 20% epoxidized soybean oil shows a rigid matrix with random distribution of liquid soybean droplets with a diameter in the range of 1 μπι (Figure 2). Unfortunately, at the higher temperature of 150 °C these liquid droplets do not cure fast enough with the remaining diamine to form rubbery particles, and we have been unable to prepare two-phase thermosets. Instead, soybean oil dissolves and plasticizes the rigid D G E B A matrix. One-phase homogeneous thermosets with single lower glass-transition temperatures are obtained as observed in S E M and D S C , respectively. The direct toughening of the corresponding more polar (less miscible) D D S formulations by epoxidized soybean oil is under investigation. Similar D G E B A - D D S formulations toughened by vernonia oil undergo (macro­ scopic) phase separation at 150 °C.

Figure 2. SEM micrograph of the fracture surface of DGEBA-isophorone diamine-Ε SO-20 specimen.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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RUBBER-TOUGHENED PLASTICS

We were able to obtain two-phase thermosets with rubbery soybean particles under the same curing conditions by using epoxidized soybean liquid rubber (ESR) instead of the initial pure epoxidized soybean oil. These liquid rubbers were prepared by B-staging (prepolymerization) of a stoichiometric mixture of epoxidized soybean oil and D D M at 135 °C for about 40 h as described in the "Experimental Details" section. A typical gel permeation chromatogram (GPC) of these soybean liquid rubbers is given in Figure 3. The soybean liquid rubbers contain oligomers with a broad molecular weight distribution in addition to the unreacted initial epoxidized soybean oil that appears as a sharp peak at about 25 min. The soybean particles again separated from the initial homogeneous mixture of D G E B A , diamine, and soybean liquid rubbers. The higher molecular weight of soybean liquid rubber (in comparison to that of the soybean oil) increases its incompatibility with the epoxy matrix at higher temperature. As a result, the final thermoset, after being cured at 150 °C, consists of a rigid epoxy matrix with randomly distributed small rubbery spherical soybean particles (Figures 4-10). The diamine molecules on the interface are expected to react with both the epoxy groups of the commercial epoxy resin and the unreacted epoxy groups of the epoxidized soybean rubber, and are expected to form chemical bonds between the rigid matrix and the rubbery particles. A plastification phenomenon at 150 °C, similar to the foregoing description for the pure epoxidized soybean oil, occurred under one-stage curing conditions for certain formulations based on soybean liquid rubbers as well. This phenomenon was observed for formulations whose epoxy matrix and soybean rubbery phase had similar solubility parameters. Such formulations are based on less polar diamines like D D M ; for example, the formulations based on D G E B A , D D M , and epoxidized soybean liquid rubber, which are abbreviated here as D G E B A - D D M - E S R . Complete miscibility and homogeneous one-phase thermosets were obtained for these formulations at any soybean liquid rubber content if one-stage curing was carried out directly at high temperatures (for instance at 150 °C). Under the higher temperature conditions, the remaining epoxy groups of the soybean liquid rubber had higher reactivity and probably copolymerized with D G E B A without phase separation. We have avoided the plastification of the D G E B A - D D M - E S R formulations and have prepared their two-phase final thermosets, which contain 15, 20, and 3 0 % soybean liquid rubber ( D G E B A - D D M - E S R - 1 5 , D G E B A - D D M - E S R - 2 0 , and D G E B A - D D M - E S R - 3 0 ) , by a two-stage curing procedure (see the Experimental Details section). The curing is carried out initially at a low temperature (70 °C) at which the soybean epoxy groups have very low reactivity. The low reactivity occurs because the soybean epoxy groups require higher curing temperatures. Practically, at 70 °C only D G E B A reacts with the diamine and free hydroxyl groups, which increase the matrix

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

1

9

ft-

1

6

s

-g

α

Ό

M

ο

5

S

η

*a S

CO

CD

Figure 3. Gel permeation chromatograms of epoxidized soybean oil (a) and liquid rubber (b). ft

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Figure 4. SEM micrograph of the fracture surface of DGEBA-DDM-ESR-15 specimen.

Figure 5. SEM micrograph of the fracture surface of DGEBA-DDM-ESR-20 specimen.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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FRISCHINGER AND DIRLIKOV Epoxidized Soybean Oil

461

Figure 6. SEM micrograph of the fracture surface of DGERA-DDM-ESR-30 specimen.

Figure 7. SEM micrograph 'of the fracture surface of DGEBA-DDS-ESR-10 specimen.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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RUBBER-TOUGHENED PLASTICS

Figure 8. SEM micrograph of the fracture surface of DGEBA-DDS-ESR-20 specimen.

Figure 9. SEM micrograph of the fracture surface of DGEBA-DDS-ESR-30 specimen used for tensile measurements.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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FRISCHINGER AND DIRLIKOV Epoxidized Soybean Oil

463

Figure 10. SEM micrograph of the fracture surface of DGEBA-DDS-ESR-30 specimen used for fracture toughness measurements. polarity, are formed. The molecular weight of the D G E B A gradually increases and the rigid cross-linked matrix is formed at 70 °C. Higher molecular weight, cross-linking, and increased polarity in the D G E B A result in higher incompatibility with the less polar hydrophobic epoxidized soybean liquid rubber, which separates into small rubbery particles at this stage. During the second curing stage, the temperature is increased to 150 °C and the less reactive soybean epoxy groups cure with the remaining diamine and form rubbery particles; the matrix post-cures simultaneously. Thus, the two-stage curing procedure allows thermodynamic equihbrium (phase separation) to be achieved Mnetically. The formulations containing only 10% soybean liquid rubber ( D G E B A - D D M - E S R - 1 0 ) , however, produce a completely transparent onephase material even following the two-stage curing procedure. Obviously, only plastification of the D G E B A epoxy rigid matrix without phase separation occurs at low soybean liquid rubber concentration. We have not been able to obtain two-phase thermosets in this case. The solubility of the soybean liquid rubber in the D G E B A - D D M resin, however, is limited. The formulations with 10% soybean rubber are closjed to saturation and we observe phase separation at shghtly higher soybean content (15%). Comparison of the D G E B A - D D M formulations toughened by epoxidized soybean oil (ESO) and rubber (ESR) at a 10% level shows that D G E B A - D D M - E S O - 1 0 forms a two-phase thermoset with small hquid soybean oil droplets at 70 °C. However, the droplets dissolve in the

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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RUBBER-TOUGHENED PLASTICS

D G E B A - D D M matrix and form a homogeneous thermoset at 150 °C. In contrast, the D G E B A - D D M - E S R - 1 0 formulation does not phase-separate, but forms a homogeneous casting at both 70 and 150 °C. The epoxidized soybean rubber is more polar than the epoxidized soybean oil due to its free hydroxyl and amine groups, and obviously it has better solubility in the D G E B A - D D M matrix at 70 °C despite its higher molecular weight. This plastification phenomenon was not observed for formulations based on diamines more polar than D D M , for instance, those based on D D S . In the D D S formulations (abbreviated, analogously, D G E B A - D D S - E S R ) the solubility parameters of the polar epoxy matrix and nonpolar soybean phase were quite different and the phase separation occurred at a lower conversion. DDS-based formulations, therefore, do not require a two-stage curing procedure to build the molecular weight of the matrix at lower temperature and increase the incompatibility between D G E B A and soybean phases. D D S formulations form two-phase thermosets directly in a one-stage curing procedure at a high temperature (150 °C) (see the "Experimental Details" section). Several factors control phase separation: Miscibility of the initial formulation of epoxy resin, amine, and epoxidized soybean oil or its liquid rubber is required. Incompatibility and phase separation should start during the curing process before gelation for spherical morphology formation. Simultaneously, the viscosity at this stage and the rate of cure should be high enough to prevent coalescence and macroscopic phase separation. The effective rubbery phase depends on the volume fraction of epoxidized soybean rubber; the degree of its B-staging; the nature (polarity, reactivity, molecular weight, etc.) of the epoxy resin and curing amine; and the time and temperature of the curing regime (kinetic factor). The introduction of the epoxidized soybean liquid rubber into the D G E B A epoxy resin has obvious advantages for preparation of two-phase thermosets over the pure epoxidized soybean oil. The soybean liquid rubber was prepared by B-staging (prepolymerization) the epoxidized soybean oil with D D M (at 135 °C for ~ 40 h) under conditions at which an advanced degree of B-staging was achieved and the conversion was just below the gel point. Therefore, the soybean liquid rubber required a very short time at 150 °C to reach its gel point and cross-link. The cross-linked soybean liquid rubber was not able to dissolve into the matrix. Obviously, the monomelic epoxidized soybean oil requires a much longer time under the same conditions to reach the equivalent gel point. Thus, the lower level of matrix plastification in the presence of soybean liquid rubber, in comparison to the soybean oil, was probably due to two factors: higher molecular weight and incompatibility at higher temperature (thermodynamic factor) and rapid cross-linking at 150 °C (kinetic factor). As mentioned earlier, the epoxidized soybean liquid rubber is a heterogeneous mixture of liquid oligomers and it contains a certain amount of the unreacted starting epoxidized soybean oil (Figure 3). No doubt, the

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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unreacted soybean oil has a stronger plastification effect on the matrix than the higher molecular weight oligomers of ESR.

Particle Size. The average particle size of the rubbery soybean phase was determined by scanning electron microscopy simultaneously with the morphology as described i n the preceding section. The average range of particle size distribution for the D G E B A - D D M - E S R and D G E B A - D D S E S R formulations is given i n Table I. Both the minimum and the maximum values are fisted. As previously mentioned, D G E B A - D D M - E S R formulations with 10% soybean hquid rubber content form homogeneous castings without separation of a second rubbery phase. The particle size of the D G E B A - D D M - E S R formulations with 15 and 20% soybean hquid rubber is in the range from 0.1 to 0.5 μπι and it increases slightly to 0.8 μηι at 30% rubber content (Table I and Figures 4-6). D D M thermosets at any soybean rubber content are characterized by a unimodal particle size distribution. The D G E B A - D D S - E S R formulations with 10% soybean hquid rubber form two-phase thermosets with ~ 1-2-μ m particle size (Table I). With 20% soybean rubber, the particle size increases and ranges from 1-5 μπι. D G E B A - D D S - E S R - 1 0 and D G E B A - D D S - E S R - 2 0 formulations are char­ acterized by relatively unimodal size distributions as well (Figures 7 and 8). The average particle size and unimodal distribution i n both D G E B A D D M - E S R and D G E B A - D D S - E S R formulations are quite reproducible with the exception of D G E B A - D D S - E S R - 3 0 at a 30% soybean content. S E M micrographs show that the average size, range, and mode of distribution of the rubbery particles in this D G E B A - D D S - E S R - 3 0 formulation are not reproducible and vary from specimen to specimen. Some specimens, for instance those used for tensile measurements, are characterized by a very Table I. Average Range of Soybean Particle Size Distribution of the Rubber-Modified DGEBA-DDM-ESR and DGEBA-DDS-ESR Thermosets Thermoset Formulation

Particle Size (p,m)

DGEBA-DDM-ESR-10

No phase separation

DGEBA-DDM-ESR-15

0.1-0.5

DGEBA-DDM-ESR-20

0.1-0.4

DGEBA-DDM-ESR-30

0.1-0.8

DGEBA-DDS-ESR-10

1-2

DGEBA-DDS-ESR-20 DGEBA-DDS-ESR-30 DGEBA-DDS-ESR-30

1-5 E

1 7

1-17 5-10, 100-200

Tensile specimens. Fracture toughness specimens.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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466

RUBBER-TOUGHENED PLASTICS

broad unimodal distribution with particle sizes ranging from 1-17 μπι (Table I and Figure 9). A bimodal particle distribution, however, is often observed for this formulation as well. For example, the specimens used for determina­ tion of fracture toughness show a bimodal size distribution with smaller particles in the range of 5-10 μ m and larger particles in the range of 100-200 μπι (Table I and Figure 10). S E M micrographs of the formulations with such bimodal particle distributions show that not only are the average size and range of the particles not reproducible, but also the apparent volume fraction varies from specimen to specimen without change in the overall morphology. As a matter of fact, the apparent volume fraction of the rubbery phase, observed on the S E M micrographs of the D G E B A - D D S - E S R - 3 0 formulations with both unimodal and bimodal particle size distribution, is greater than the actual volume soybean fraction. The increased volume fraction indicates (1) that the larger particles in the D G E B A - D D S - E S R - 3 0 formulations with bimodal distribution are the result of occlusion of the D G E B A epoxy component into the soybean rubbery particles and (2) are in close proximity to the phase-inversion point at 30% soybean rubber. Such phase-inversion phenomena were observed by Lee et al. (10) for a similar formulation, D G E B A - D D S - C T B N at a high 30% C T B N liquid rubber content. Recently, we experimentally confirmed the phase-inversion phenomena and the occlusion of D G E B A resin in the rubbery particles in a similar formulation, D G E B A - D D M - v e r n o n i a rubber at 20% vernonia rubber, by S E M micrographs of specimens treated with osmium tetraoxide (unpublished data). In contrast to the epoxidized soybean oil, vernonia oil contains carbon-carbon double bonds, stains with osmium tetraoxide, and its rubbery phase is easily distinguished from the D G E B A resin in S E M micrographs. The miscibility and phase separation in close proximity to the phaseinversion point are highly dependent on the kinetic factors. A small devia­ tion in temperature or time of the curing process causes a shift in the phaseinversion point, broad variation of morphology for different specimens, and fluctuation of physicomechanical properties, as will be discussed later. It is not clear, however, why D G E B A - D D S - E S R - 3 0 results in a bi­ modal distribution (in some specimens) and appears to be close to the phase-inversion point, whereas the corresponding D G E B A - D D M - E S R - 3 0 with the same soybean rubber content does not exhibit these phenomena. The differences are probably due to two factors. First, different curing procedures were used for the D G E B A - D D M E S R and D G E B A - D D S - E S R formulations. The D G E B A - D D S - E S R - 3 0 formulation was cured directly for 2 h at 150 °C. The D G E B A - D D M - E S R 30 was cured according to a two-stage curing procedure: first at 75 °C for 4 h and then at 150 °C for 2 h. As previously discussed, the two-stage procedure allows the matrix formation at a lower temperature and results in better separation of the soybean rubber (perhaps without D G E B A occlusion).

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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19.

FRISCHINGER AND DIRLIKOV Epoxidized Soybean Oil

467

Direct comparison of the morphology and rubbery particle size and distribu­ tion of D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations pre­ pared under the same curing conditions is difficult. D D S has a high melting point (mp = 177 °C) and requires a higher temperature (> 130 °C) to dissolve in the initial D G E B A - E S R formulation and form homogeneous mixtures. D G E B A - D D S - E S R formulations, therefore, cannot be cured by the two-stage procedure, but were cured directly in one stage at a higher temperature (150 °C). In contrast, D D M has a lower melting point (mp = 91 °C) and its initial D G E B A - D D M - E S R formulations are homogeneous mixtures at much lower temperature. D D M formulations, however, are more compatible and form only one-phase thermosets without phase separation by the direct one-stage curing procedure at a high temperature (150 °C). Second, the formation of larger rubbery particles and D G E B A occlusion at the phase-inversion point depends on the mutual miscibility of D G E B A resin and soybean rubber, and especially depends on the solubility partition constants of the D G E B A monomer in the matrix and in the rubbery phase at different stages of curing. The D G E B A - D D M - E S R and D G E B A - D D S E S R formulations are characterized by different miscibility. At an earlier stage of curing, the initial unreacted (nonpolar) D G E B A monomer of the D G E B A - D D S - E S R formulations, especially those with a higher E S R con­ tent, has a relatively higher solubility in the nonpolar E S R rubber phase than in the highly polar DDS-dominated D G E B A - D D S "matrix" phase, which is characterized by strong hydrogen bondings between amine, hydroxyl, and sulfone groups. [As a matter of fact, the D G E B A monomer is miscible at any ratio at room or elevated (70 °C) temperature with the epoxidized soybean rubber, but is completely insoluble in DDS.] The D G E B A monomer, dis­ solved in the rubbery phase, reacts with the diamine over progressing cure time and phase-separates at a later stage with the formation of small rigid particles within the large rubbery particles. Therefore, we observe much larger particles (100-200 μπι), greater apparent rubbery volume fraction (than the actual soybean volume fraction), and the phase-inversion phe­ nomenon at a relatively lower soybean content (at ~ 30%) for the D G E B A - D D S - E S R formulations. In contrast, the D G E B A monomer of the D G E B A - D D M - E S R formulations has relatively lower solubility under the same conditions in the rubbery phase because the D G E B A - D D M "matrix" phase is much less polar than the D G E B A - D D S phase. As a matter of fact, the D G E B A monomer is miscible with D D M at a much lower temperature. As a result, the rubbery particles of the D G E B A - D D M - E S R - 3 0 formulation do not contain smaller rigid D G E B A particles even at 30% soybean rubber and their apparent volume fraction corresponds to the actual soybean con­ tent. The formation of larger particles and the phase-inversion phenomenon for the D D M formulations is expected to occur at a higher soybean content. Phase diagrams of both formulations and further S E M evaluation on the fracture surface of these thermosets are under investigation. Similar miscibil-

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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468

RUBBER-TOUGHENED PLASTICS

ity phenomena have been reported by Romanchick et al. (II) for C T B N modified D G E B A epoxy resins. The S E M micrographs of all D D M - and DDS-based formulations with 10, 15, 20, and 30% soybean content display rough fracture surfaces. Evi­ dently, the soybean rubbery particles cavitate under shear (fracture) deforma­ tion with the formation of deep voids (Figures 4-9). A comparison of both formulations shows rougher fracture surface and less pronounced cavitation phenomena in the D G E B A - D D S - E S R formulations. Some of the D G E B A - D D S - E S R particles are clearly observed in S E M , but only a portion of the particles have cavitated with the formation of some deep voids. The cavitation process is much more efficient in the smaller rubbery particles of D G E B A - D D M - E S R formulations where complete cavitation and a smoother fracture surface are observed. The results also show that D G E B A - D D S - E S R and D G E B A - D D M ESR formulations are characterized by different particle sizes at the same soybean rubber content (Table I), which indicates that the particle size depends on the compatibility of the formulations. The D G E B A - D D M - E S R formulations are expected to have better compatibility than the D G E B A - D D S - E S R formulations because both the D G E B A epoxy matrix and the soybean rubber phase are based on the same D D M diamine. In addition, D D M is less polar than D D S . The solubility parameter of the D D M matrix in the D G E B A - D D M - E S R formulations, therefore, matches the solubility parameter of the nonpolar soybean liquid rubber much better than the more polar D D S matrix in the D G E B A D D S - E S R formulations. As a result of better compatibility, the D G E B A D D M - E S R formulations with a 10% soybean content form homogeneous thermosetting material without phase separation. The rubbery particles ob­ served in the formulations with 15, 20, and 30% soybean rubber are formed at a later stage in curing and have a smaller diameter. The D G E B A - D D S - E S R formulations are less compatible because (1) they are based on two different diamines—DDS in the rigid matrix and D D M in the rubbery phase—and (2) their D D S matrix is more polar (see preceding text). The D G E B A - D D S - E S R formulations, therefore, are char­ acterized by bigger rubbery particles that separate at earlier stages of curing from the initial liquid homogeneous mixture. In comparison with D G E B A D D M - E S R formulations, the particle size of D G E B A - D D S - E S R formula­ tions increases much more rapidly with increasing soybean rubbery content, especially in close proximity to the phase-inversion point, due to D G E B A occlusion (Table I). The foregoing results show that under the same curing conditions, but using different diamines, the particle size of the rubbery phase in the range of desirable particle size for toughening epoxy thermosets (e.g., ranging from 0.1 to 10 μπι) can be varied easily. In general, larger particles (and even macroscopic total phase separation) were observed for less compatible formu-

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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19.

FRISCHINGER AND DIRLIKOV Epoxidized Soybean Oil

469

lations with more polar diamines used for curing the rigid matrix, for instance D D S . In addition, a lower viscosity of the formulations (at higher temperature) allows coalescence of the hquid soybean droplets and results in the formation of bigger rubbery particles. In contrast, higher curing rates result in rapid cross-hnking, prevent coalescence, and thus produce smaller rubbery particles. In summary, the particle size depends on the nature of the diamines used for curing the matrix and for preparation of the soybean hquid rubber; the volume fraction of the epoxidized soybean rubber; the degree of B-staging of the soybean rubber; the viscosity of the formulations and rate of cure (e.g., temperature and time of B-staging); the cure of the final thermoset (cure kinetics); and so forth.

Class-Transition Temperature. The temperature dependence of the storage modulus and tangent delta of the two "pure" matrices— D G E B A - D D M and D G E B A - D D S — w e r e determined by dynamic mechanical analysis in the temperature range of —130 to +200 °C (Figures 11-14). Both thermosets were prepared without soybean rubber under the same curing conditions as the corresponding two-phase materials in the presence of soybean rubber. The glass-transition temperatures, T , of these one-phase D G E B A - D D M and D G E B A - D D S thermosets were observed at 190 and 185 °C, respectively. In addition, the D G E B A - D D M and D G E B A - D D S thermosets exhibited beta relaxations at lower temperatures: —30 and —35 °C, respectively (Table II). We were unable to measure the D M A of the pure epoxidized soybean rubber (ESR) cured under the same conditions in the absence of the D G E B A - d i a m i n e component. The E S R glass-transition temperature (T = — 25 °C) was determined by differential scanning calorimetry (Figure 15 and Table II). Obviously, the E S R thermoset exists i n a rubbery state at room temperature, and it appears to be suitable for toughening commercial (brittle) epoxy resins. The temperature dependence of the storage modulus and tangent delta of both D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations at different contents of soybean hquid rubber was determined by D M A (Figures 12-15). A l l formulations exhibited transitions at high and low temperatures (Table II). The higher temperature transitions of the D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations occur i n close proximity to the glasstransition temperature of the pure D G E B A - D D M and D G E B A - D D S thermosets: i n the range of 145-190 °C. Therefore, these transitions were assigned to the glass-transition temperatures of their D G E B A matrices. These glass-transition temperatures gradually decrease i n the corresponding g

g

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

Figure 11. DMA temperature dependence of the storage dynamicflexuremodulus, E', of a pure DGEBA-DDM thermoset (A) and its rubber-modified DGEBA-DDM-ESR formulations at 15% (B), 20% (C), and 30% (D) rubber content.

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993. 250

Figure 12. DMA temperature dependence of the storage dynamicflexuremodulus, E', of a pure DGEBA-DDS thermoset (A) and its rubber-modified DGEBA-DDS-ESR formulations at 10% (B), 20% (C), and 30% (D) rubber content.

Temperature (°C)

Amplitude (p-p) = 0.20 mm

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

Figure 13. DMA tangent delta and dynamic mechanical damping peaks of a pure DGEBA-DDM thermoset (A) and its rubber-modified DGEBA-DDM-ESR formulations at 15% (B), 20% (C), and 30% (D) rubber content

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

Figure 14. DMA tangent delta and dynamic mechanical damping peaks of a pure DGEBA-DDS thermoset (A) and its rubber-modified DGEBA-DDS-ESR formulations at 10% (B), 20% (C), and 30% (D) rubber content.

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RUBBER-TOUGHENED PLASTICS

474

Table II. DMA Lower and Higher Temperature Transitions of Pure DGEBA-DDM and DGEBA-DDS Thermosets and Their Rubber-Modified DGEBA-DDM--ESR and DGEBA-DDS-ESR Formulations Transition (°C)

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Thermoset Formulation

Low

High

DGEBA-DDM DGEBA-DDM-ESR-15 DGEBA-DDM-ESR-20 DGEBA-DDM-ESR-30

-30 -35 -33 -39

190 161 165 145

DGEBA-DDS DGEBA-DDS-ESR-10 DGEBA-DDS-ESR-20 DGEBA-DDS-ESR-30

-35 -45 -43 -30

185 168 166 161

ESR

-25

a

C

b

The lower transition temperature corresponds to an overlap in the glass-transition temperature of the rubbery particles and beta transition of the D G E B A matrix. Glass-transition temperature of the D G E B A matrix. Determined by DSC.

a

c

D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations with an i n creasing amount of soybean hquid rubber. Obviously, a part of the soybean rubber, and especially its lower molecular weight oligomers and its unreacted epoxidized soybean oil, dissolves and plasticizes the D G E B A rigid matrix. This plastification phenomenon is more pronounced for the D G E B A D D M - E S R formulations. The depression of the glass-transition temperature of the D G E B A - D D M - E S R matrices is about 25 °C at 15-20% of soybean rubber content and almost 45 °C at 30% loading. As discussed in the preceding section, the D G E B A matrix and soybean rubber are characterized by better compatibility in the D D M formulations than i n those based on D D S . This compatibility results in better plastification and high concentration of soybean rubber in the D G E B A phase, both of which are confirmed here by greater depressions observed for the glass-transition temperature of the D D M matrices. Smaller depressions of the matrix glass-transition temperature are observed for the less compatible D G E B A - D D S - E S R formulations. The D D S formulation T decreases from about 15 °C at 10% soybean hquid rubber to - 25 °C at 30% loading. The lower temperature transitions of the D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations are observed in the range —30 to — 45 °C. No other transitions for these formulations are detected, either at a higher temperature in the range of — 30 to +130 °C or at a lower temperature in the range of —45 to —130 °C. Therefore, we believe that the glass-transition temperature of the E S R rubbery particles and the beta transition of the matrix of the two-phase formulations overlap in the range of g

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

X

10

5 Ο

-0.4-150

-0.2H

0.0-

0.2H

0.4H

-50 Temperature

0 C°C)

-r

Figure 15. DSC curve of epoxidized soybean liquid rubber.

-100

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50

si

Ci

es*

C/3

Su

tu > d

οw

Ω

RUBBER-TOUGHENED PLASTICS

476

— 30 to — 45 °C and are observed as a single transition at a lower temperature. The glass-transition temperature of the rubbery particles in the two-phase thermosets was expected to correspond to that of the pure E S R rubber or to appear at a slightly higher temperature if the rubbery particles dissolved a certain amount of D G E B A epoxy component that had a higher T . Surprisingly, the low transition temperatures of the two-phase thermosets are observed at a slightly lower temperature than the glass-transition temperature of the pure E S R rubber. This discrepancy is probably due to the different methods used for determination of these transitions: D M A is used for the two-phase thermosets and D S C is used for the pure E S R rubber. The discrepancy might also result as an artifact of the overlapping of the glass transition of the rubbery particles and the beta transition of the matrix or from stresses induced by thermal shrinkage as discussed by Manzionne and Gillham (12). The slight increase of the lower temperature transition observed for the D G E B A - D D S - E S R - 3 0 formulation with bimodal particle size distribution could be attributed to the occlusion of epoxy D G E B A resin into the larger rubbery particles. In any case, the glass-transition temperature of the pure soybean rubber (ESR) does not change much in the presence of the D G E B A matrix in both D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations. The relatively constant T indicates that the rubber phase in these two-phase thermosets does not contain a significant amount of the D G E B A component below the phase-inversion point and the thermosets are formed practically by pure soybean rubber.

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g

g

F r a c t u r e T o u g h n e s s . The fracture toughness, in terms of the stress intensity factor, K , and fracture energy, G , is given in Table III for both D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations. I c

I c

Table III. Stress Intensity Factor, K , and Fracture Energy, G , of Pure DGEBA-DDM and DGEBA-DDS Thermosets and Their Rubber-Modified DGEBA-DDM-ESR and DGEBA-DDS-ESR Formulations I c

Thermoset Formulation

I c

(MPa * m ) l/2

(J/m ) 2

0.75

175

DGEBA-DDM-ESR-15

1.24

564

DGEBA-DDM-ESR-20

1.33

802

DGEBA-DDM-ESR-30

1.40

1008

DGEBA-DDS

0.75

145

DGEBA-DDS-ESR-10

1.09

374

DGEBA-DDS-ESR-20

1.19

596

DGEBA-DDS-ESR-30

0.54

145

D G E B A - D D M DGEBA-DDM-ESR-10

a

a

This formulation does not phase-separate and its fracture toughness has not been determined.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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19.

FRISCHINGER AND DIRLIKOV Epoxidized Soybean Oil

477

A better toughening effect, which gradually increases at a higher soybean content, is observed for the D G E B A - D D M - E S R formulations. The plasti­ fication phenomenon that occurs at a larger scale for these formulations (see the two preceding sections) probably affects the improved toughening via the soybean component, which acts as a matrix plastieizer. These formulations also are characterized by smaller particle size (Table I; 0.1-0.8 μπι), and their fracture surfaces show extensive particle cavitation and formation of deep voids (see the "Particle Size" section and Figures 4-6). Pearson and Yee (13) have shown that the toughening mechanism of elastomer-modified epoxies is governed by the phenomena of internal cavitation of rubber particles and formation of shear bands. The efficiency of these mechanisms depends on rubber particle size. Pearson and Yee also demonstrated that smaller particles ranging from 0.2-2 μ m are more efficient and produce a better toughening effect than larger particles. The higher values for fracture energy observed for the D G E B A - D D M - E S R formulations are probably due to both better compatibility (plastification) and smaller particles (in the range from 0.1-0.8 μπι; Table I) with a more efficient toughening mechanism. A smaller improvement of fracture toughness is observed for the D G E B A - D D S - E S R formulations. Plastification plays a smaller role here and the formulations are characterized by larger rubbery particles. In agree­ ment with the results of Pearson and Yee, the larger particles act as "bridging" particles with only a modest increase in fracture toughness. In addition, D G E B A - D D S - E S R formulations exhibit optimum toughening at 20% soybean component. The D G E B A - D D S - E S R - 3 0 specimens at 30% soybean hquid rubber, which were used here for determination of fracture toughness, are characterized by bimodal particle size distribution and are close to their phase-inversion point (see the "Particle Size" section). Physicomechanical properties of epoxy resins start to deteriorate rapidly at the phase-inversion point and, therefore, we observe lower fracture toughness for the D G E B A - D D S - E S R - 3 0 thermoset. In summary, our measurements show that the introduction of soybean hquid rubber remarkably improves the fracture toughness of commercial highly cross-linked brittle epoxy resins, such as D G E B A - D D S and D G E B A - D D M , which exhibit low ductility and, as shown by other authors (14, 15), are very difficult to toughen.

Tensile Properties. Young's moduli were determined from the cor­ responding tensile stress-strain curves. The Young's moduli are reported here as an average value of several independent tensile measurements to minimize the fluctuations observed in our tensile data as a result of the high stiffness of the specimens (Table IV). The dependence of Young's modulus on the soybean content is plotted in Figure 16 for both D G E B A - D D M - E S R and D G E B A - D D S - E S R formula­ tions. As expected, the elastic moduli gradually decrease with increasing

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

RUBBER-TOUGHENED PLASTICS

478

Table IV. Young's modulus, E , of pure DGEBA-DDM and DGEBA-DDS Thermosets and Their Rubber-Modified DGEBA-DDM-ESR and DGEBA-DDS-ESR Formulations Thermoset Formulation

Ε

(MPa)

DGEBA-DDM

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DGEBA-DDM-ESR-10

2840 F L

DGEBA-DDM-ESR-15

2410

DGEBA-DDM-ESR-20

1950

DGEBA-DDM-ESR-30

1720

DGEBA-DDS

3420

DGEBA-DDS-ESR-10

2810

DGEBA-DDS-ESR-20

2100

DGEBA-DDS-ESR-30

1780

a

This formulation does not phase-separate and its tensile properties have not been determined.

Σ 1000

500 0 -I

1

1

j

j

1

1-

0

5.

10

15

20

25

30

ESR Rubber, % Figure 16. Dependence of Young's modulus on the ESR rubber content of the DGEBA-DDM-ESR (A) and DGEBA-DDS-ESR formulations (B). soybean fraction. Linear relationships can approximately fit the different points for both formulations, and a slight deviation is observed only with a higher content of soybean rubber. The slope of the D G E B A - D D S - E S R formulations, however, is steeper than that of D G E B A - D D M - E S R . The tensile properties of D G E B A - D D S - E S R decrease faster with increasing

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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19.

FRISCHINGER AND DIRLIKOV

Epoxidized Soybean Oil

479

soybean content. This result may be attributed to the larger rubbery particles of the D G E B A - D D S - E S R formulations. Surprisingly, the linear tensile dependence of the D G E B A - D D S - E S R formulations on the soybean rubber content does not correlate well with the corresponding fracture toughness relationship, which shows an optimum at 20% and a drop in fracture toughness at 30% soybean content. As discussed in the "Particle Size" section, the D G E B A - D D S - E S R formulation at 30% soybean content is close to its phase-inversion point and its different speci­ mens have different morphology. Indeed, direct comparison of the S E M micrographs on the fracture surface of the D G E B A - D D S - E S R - 3 0 formula­ tion shows that the tensile specimens used in this study are characterized by a unimodal particle size distribution ranging from 1-17 μπι (Table I and Figure 9). In contrast, the specimens used for fracture-toughness measure­ ments show a bimodal distribution with smaller particles ranging from 5-10 μ m and larger particles ranging from 100-200 μ m (Table I and Figure 10). The different morphology of the D G E B A - D D S - E S R - 3 0 specimens used for tensile and fracture-toughness measurements obviously results in fluctuation of their physicomechanical properties.

Water Absorption. High water absorption is another major disad­ vantage of the commercial epoxy resins in addition to their poor fracture toughness. The maximum water absorption of the D G E B A - D D S - E S R and D G E B A - D D M - E S R formulations was determined on predried samples immersed in boihng water until saturation (constant weight) as described in the "Experimental Details" section. Although our results are somewhat lower than expected, the water absorption of both formulations decreases gradually and linearly with increasing soybean content (Table V). Obviously, the highly hydrophobic long fatty chains of the epoxidized soybean oil reduce the water Table V. Maximum Water Absorption of Pure DGEBA-DDM and DGEBA-DDS Thermosets and Their Rubber-Modified DGEBA-DDM-ESR and DGEBA-DDS-ESR Formulations Thermoset Formulation

Water Absorption (%)

DGEBA-DDM

2.42

DGEBA-DDM-ESR-15 DGEBA-DDM-ESR-20

2.22

DGEBA-DDM-ESR-30

2.00 1.62

DGEBA-DDS DGEBA-DDS-ESR-10 DGEBA-DDS-ESR-20

3.61 3.33 3.13

DGEBA-DDS-ESR-30

2.80

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

480

RUBBER-TOUGHENED PLASTICS

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absorption of the epoxy thermosets. As expected, the D G E B A - D D S - E S R formulations at different soybean hquid rubber content have a higher water absorption than the corresponding D G E B A - D D M - E S R formulations, due to the more polar character of D D S in comparison to D D M .

Dielectric Properties. The dielectric constants and dissipation factors of the D G E B A - D D M - E S R and D G E B A - D D S - E S R formulations are given in Table V I . The introduction of epoxidized soybean oil, with its long aliphatic chains, was expected to lower the dielectric constant and dissipation factor of the commercial epoxy resins simultaneously, despite the formation of free hydroxyl groups by the opening of the epoxy rings. Surprisingly, the dielectric properties of both types of formulations do not change (decrease) much with increasing soybean hquid rubber content. Although we do not have an explanation for this observation at the present moment, D . Shimp (Rhone-Poulenc, personal communication) has suggested that, in addition to the traditional epoxy curing reaction, the epoxidized soybean oil (and rubber) might undergo amidolysis with the aromatic D D S or D D M diamines under our curing conditions. As demonstrated in Scheme I, the amidolysis proceeds via the formation of additional glycerol free hydroxyl groups and fatty acid amide groups, both with very high dielectric properties. These by-products increase the dielectric constant and dissipation factor of their two-phase thermosets and balance the reduction effect of the long aliphatic chains of the epoxidized soybean oil. To prove that such amidolysis takes place, we measured consecutive infrared spectra of a stoichiometric mixture of epoxidized soybean oil and D D M with progressing B-staging time (Figure 17). B-staging (or prepolymerization) was carried out at 135 °C for 48 h under conditions similar to those at which the castings used for determination of the dielectric properties were prepared. The infrared spectrum of the initial pure epoxidized soybean oil exhibited a single absorption band at about 1730 c m that corresponds to - 1

Table VI. Dielectric Properties of Pure DGEBA-DDM and DGEBA-DDS Thermosets and Their Rubber-Modified DGEBA-DDM-ESR and DGEBA-DDS-ESR Formulations Thermoset Formulation

Dissipation Factor (X10~ ) 2

Dielectric Constant

DGEBA-DDM DGEBA-DDM-ESR-15 DGEBA-DDM-ESR-20 D G E B A - D D M - E S R 30

3.3 3.5 3.6 3.7

3.78 3.78 3.77 3.77

DGEBA-DDS DGEBA-DDS-ESR-20

2.5 3.3

3.95 3.88

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

FRISCHINGER AND DIRLIKOV

19.

Epoxidized Soybean Oil

481

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

Figure 17. Infrared spectra of pure epoxidized soybean oil (A) and its liquid rubbers with DDM after prepolymerization at 135 °Cfor 0 (B), 24 (C), and 48 h (D). Continued on next page.

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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486

RUBBER-TOUGHENED PLASTICS

the stretching > C = Ο vibrations of the E S O carbonyl — C O O groups. A comparison of this infrared spectrum with the spectrum of the B-staged materials with progressing B-staging time reveals no new absorption bands for the > C = Ο vibrations of the amide — C O O N H groups of the by-prod­ uct nor any other changes in the region of 1800-1650 c m . The comparison results indicate that if the amidolysis reaction indeed proceeds simultaneously with the traditional epoxidation reaction, it does so only to a limited extent.

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- 1

Sodium Content. Low ionic content, often below 10 ppm (especially for sodium and chlorine ions) is a requirement for the application of epoxy resins i n the electronics industry. Electronics-grade epoxy resins are signifi­ cantly more expensive because an additional purification procedure is needed to lower ionic content. Epoxidized soybean oil and liquid rubber, without any purification, is characterized by very low sodium content (16.5 and 12.5 ppm, respectively). The content of other ionic species is probably also low. The hydrophobic nonpolar molecular structure of the epoxidized soybean oil, which lacks free hydroxyl or carboxyl groups, is probably responsible for low ionic content. Thus, epoxidized soybean rubber appears especially suitable for toughening epoxy resins for electronics applications. Epoxidized Soybean Oil vs. Vernonia Oil.

In general, the mor­

phology, particle size, toughening, and so forth of D G E B A - D D M and D G E B A - D D S epoxy formulations modified by epoxidized soybean oil or rubber resemble the characteristics of the corresponding two-phase ther­ mosets based on vernonia oil and rubber (8) prepared under similar condi­ tions. A comparison of the effect of the two oils also shows several differ­ ences. Although vernonia oil has a structure similar to that of the epoxidized soybean oil, it is characterized by a lower epoxy functionality. Vernonia oil contains an average of 2.4 epoxy groups per triglyceride molecule, which is only half of the average 4.5 epoxy groups found in epoxidized soybean oil. Vernonia oil and rubber, therefore, is expected to have less polar character than the epoxidized soybean oil and rubber, to have lower compatibility with commercial epoxy resins, and to produce rubbery particles with lower crossfinking density. Our results (8) agree with the projections and show the formation of bigger vernonia particles whose separation proceeds at an earlier stage of B-staging and curing of the vernonia formulations of commercial epoxy resins. For example, the D G E B A - D D M formulation containing 10% vernonia rubber forms two-phase thermosets, whereas the corresponding D G E B A - D D M - E S R - 1 0 is homogeneous. In addition, vernonia rubbery particles have a lower glass-transition temperature, which reflects lower cross-hnked density. These results show that the morphology, particle size, and, presumably, the fracture toughness (together with the other physicomechanical proper-

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

19.

FRISCHINGER AND DIRLIKOV

Epoxidized Soybean Oil

487

ties) of the commercial epoxy resins can be varied not only by changing the nature and polarity of the diamine curing agent as discussed previously, but also can be altered by variation of the nature and degree of epoxidation of the vegetable oils.

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Epoxidized Vegetable Oils vs. CTBN Liquid Rubber. It is also interesting to compare the effect of epoxidized vegetable oils with the effect of C T B N hquid rubber, which presently is commonly used for epoxy toughening. For this purpose, we compared our results on D G E B A - D D S ESR-10 with published data (14) on the D G E B A - D D S thermoset modified with 10% C T B N ( D G E B A - D D S - C T B N - 1 0 ) . Although both thermosets were prepared by different procedures, they had similar morphology. C T B N was incorporated into the epoxy resin without prepolymerization. According to recent studies by Pearson and Yee (14) on the toughening of epoxy resins, the introduction of 10% C T B N hquid rubber into a D G E B A - D D S epoxy resin produces two-phase thermosets with C T B N rubbery particles with a diameter of ~ 5 μηι. The fracture energy of the unmodified D G E B A - D D S thermoset increases from G = 162 J / m to G = 242 J / m i n the presence of 10% C T B N (e.g., with AG = 80 J/m ), whereas its Young's modulus simultaneously decreases from Ε = 3360 M P a to Ε = 3000 M P a (14). Our unmodified D G E B A - D D S thermoset exhibits fracture toughness ( G = 145 J / m ) and Young's modulus (E = 3420 MPa) (Tables III and IV) similar to those reported by Pearson and Yee (14). The corresponding soybean-modified D G E B A - D D S - E S R - 1 0 ther­ moset at the same rubber content, however, has smaller rubbery particles ranging from 1-2 μηι (Table I). The introduction of 10% soybean liquid rubber more than doubles the fracture energy of the unmodified D G E B A - D D S thermoset from G = 145 J / m to G = 374 J / m (Table III) (e.g., with A G = 229 J/m ), whereas the Young's modulus decreases from Ε = 3420 M P a to Ε = 2810 M P a (Table IV), a slightly lower value than that observed for the CTBN-modified thermoset by Pearson and Yee (14). Comparison of the toughening effect at 10% content level indicates that the soybean hquid rubber ( A G = 229 J / m ) is more effective than C T B N (AG = 87 J / m ) . Comparison of the S E M micrographs shows a relatively smooth fracture surface for the D G E B A - D D S - C T B N - 1 0 thermoset (14). In contrast, the corresponding soybean-modified D G E B A - D D S - E S R - 1 0 fracture surfaces show extensive deep voids and more pronounced particle cavitation. These phenomena are characteristic for smaller rubbery particles and result in the improved toughening effect observed for the soybean hquid rubber. Another advantage of the epoxidized soybean rubber is its low sodium content (12.5 ppm) in contrast to the higher sodium content of the C T B N (in the range of 300 ppm; R. Drake, BFGoodrich, personal communication). As a matter of fact, the sodium content of Hycar C T B N 1300 X 16 (BFGoodrich) 2

I c

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In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

2

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488

RUBBER-TOUGHENED PLASTICS

is 380 ppm (Galbraith Analytical Laboratory). Low ionic content is an important characteristic for electronics applications of liquid rubbers for the toughening epoxy resins (see the "Sodium Content" section). Reduction of the sodium content of C T B N s requires additional washing (purification). Finally, epoxidized soybean oil is industrially produced and available at about $0.50 per pound, a price below that of C T B N (in the range of $2.00-$2.50 per pound). Price alone makes the toughening of commercial epoxy resins by epoxidized soybean oil very attractive for large-scale commer­ cial apphcations. The epoxidized soybean oil appears to have three potential advantages over C T B N for toughening epoxy resins: better toughening effect, lower sodium content, and lower price.

Summary Homogeneous mixtures of epoxidized soybean rubber (and probably rubber of any other epoxidized vegetable oil), commercial epoxy resins based on diglycidyl ether of bisphenol A (Epon resin 825, etc.), and commercial diamines ( D D S , D D M , etc.) form, under certain conditions, two-phase thermosetting materials that consist of a rigid epoxy matrix and randomly distributed small rubbery particles of cured epoxidized soybean oil. Particle size varies from 0.1-5 μπι and depends on the nature of the diamine, the B-staging conditions, the kinetics of curing, and so forth. Although further research is required, our initial unoptimized results show that these two-phase thermosetting materials have toughness compara­ ble to (if not better than) the CTBN-modified epoxies, as well as lower water absorption and low sodium content; they may even be more environmentally friendly. The E S R formulations exhibit sfightly lower glass-transition temper­ atures and Young's moduli in comparison with the unmodified thermosets, but their dielectric properties do not change. Optimization of the preparation conditions is expected to further improve the physicomechanical properties of E S R formulations. Several options for direct epoxy toughening by epoxidized soybean oil, especially of D D S formulations, are under investigation. Epoxidized soybean oil is industrially produced and available at about $0.50 per pound, a price below the least expensive epoxy resins based on D G E B A ($1.25-$1.35 per pound) and much lower than the price of C T B N (in the range of $2.00-$2.50 per pound), which is commonly used for epoxy toughening. The toughening of commercial epoxy resins by epoxidized soy­ bean oils and rubbers is, therefore, very attractive for large-scale commercial apphcations.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.

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Acknowledgments The authors gratefully acknowledge A . Yee (University of Michigan) for help in obtaining the fracture toughness and tensile data; D . Shimp (Rhone-Poulenc) for measurements of dielectric properties; R. Schweizer (Paint Research Associates) for sodium content determination; and R. Pearson and S. Jin (University of Michigan) for many fruitful discussions. We gratefully acknowl­ edge the financial support of the South Coast Air Quality Management District, the U.S. Agency for International Development, Paint Research Associates, and the State of Michigan. We thank T A Instruments (formerly DuPont Instruments) for donating D S C and D M A to our Institute.

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4. Rubber-Modified Thermoset Resins; Riew, K. C.; Gillham, J. K., Eds.; Advances in Chemistry 208; American Chemical Society: Washington, D C , 1984. 5. Yee, A. F.; Pearson, R. A. J. Mater. Sci. 1986, 21, 2462. 6. Pearson, R. Α.; Yee, A. F. J. Mater. Sci. 1986, 21, 2475. 7. Qureshi, S.; Manson, J. Α.; Michel, J. C.; Hertzberg, R. W.; Sperling, L. In

Characterization of Highly Cross-Linked Polymers; Labana, S. S.; Dickie, R. Α.,

Eds.; ACS Symposium Series 243; American Chemical Society: Washington, D C , 1984; pp 109-124. 8. Dirlikov, S. K.; Frischinger, I.; Islam, M. S.; Lepkowski, T. J. In Biotechnology and Polymers; Gebelein, C. G., Ed.; Plenum Press: New York, 1991.

9. Brown, W. F.; Srawley, J. E. ASTM Spec. Tech. Publ. 1965, 381, 13.

10. Lee, W. H.; Hodd, Κ. Α.; Wright, W. W. In Rubber-Toughened Plastics; Riew, K. C., Ed.; Advances in Chemistry 222; American Chemical Society: Washington, DC, 1989; pp 263-287.

11. Romanchick, W. Α.; Sohn, J. E.; Geibel, J. F. In Epoxy Resin Chemistry II; Bauer, R. S., Ed.; ACS Symposium Series 221; Washington, D C , 1985; pp 85-118.

American Chemical Society:

12. Manzionne, L. T.; Gillham, J. K. J. Appl. Polym. Sci. 1981, 26, 889. 13. Pearson, R. A.; Yee, A. F. J. Mater. Sci. 1991, 26, 3828.

14. Pearson, R. Α.; Yee, A. F. J. Mater. Sci. 1989, 24,

2571.

15. Levita, G. In Rubber-Toughened Plastics; Riew, K. C., Ed.; Advances in Chem­ istry 222; American Chemical Society: Washington, D C , 1989; pp 93-118. RECEIVED

for review March 6, 1991.

ACCEPTED

revised manuscript June 23,

1992.

In Toughened Plastics I; Riew, C., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1993.